EP2861632A2 - Lithographic offset inks with water and filler content - Google Patents
Lithographic offset inks with water and filler contentInfo
- Publication number
- EP2861632A2 EP2861632A2 EP20130805102 EP13805102A EP2861632A2 EP 2861632 A2 EP2861632 A2 EP 2861632A2 EP 20130805102 EP20130805102 EP 20130805102 EP 13805102 A EP13805102 A EP 13805102A EP 2861632 A2 EP2861632 A2 EP 2861632A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- pigment
- ink
- pigment yellow
- water
- red
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000976 ink Substances 0.000 title claims abstract description 518
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 239000000945 filler Substances 0.000 title claims description 54
- 238000007639 printing Methods 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 71
- 230000008569 process Effects 0.000 claims abstract description 47
- 238000012546 transfer Methods 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 230000005855 radiation Effects 0.000 claims abstract description 16
- 238000001459 lithography Methods 0.000 claims abstract description 15
- 238000010894 electron beam technology Methods 0.000 claims abstract description 14
- 239000002480 mineral oil Substances 0.000 claims abstract description 10
- 239000000049 pigment Substances 0.000 claims description 272
- 239000003995 emulsifying agent Substances 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 41
- -1 ambergum Substances 0.000 claims description 27
- 239000001993 wax Substances 0.000 claims description 27
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 239000003086 colorant Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 18
- 235000019198 oils Nutrition 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000004927 clay Substances 0.000 claims description 15
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 12
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000009472 formulation Methods 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229920000180 alkyd Polymers 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 6
- 235000010469 Glycine max Nutrition 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 244000215068 Acacia senegal Species 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229920000084 Gum arabic Polymers 0.000 claims description 5
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 5
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000205 acacia gum Substances 0.000 claims description 5
- 235000010489 acacia gum Nutrition 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 150000001408 amides Chemical group 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- 150000002194 fatty esters Chemical class 0.000 claims description 5
- 239000007762 w/o emulsion Substances 0.000 claims description 5
- MXFQRSUWYYSPOC-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical class C=CC(=O)OCC(C)(C)COC(=O)C=C MXFQRSUWYYSPOC-UHFFFAOYSA-N 0.000 claims description 4
- SOFRHZUTPGJWAM-UHFFFAOYSA-N 3-hydroxy-4-[(2-methoxy-5-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound COc1ccc(cc1N=Nc1c(O)c(cc2ccccc12)C(=O)Nc1cccc(c1)[N+]([O-])=O)[N+]([O-])=O SOFRHZUTPGJWAM-UHFFFAOYSA-N 0.000 claims description 4
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 claims description 4
- FWTBRYBHCBCJEQ-UHFFFAOYSA-N 4-[(4-phenyldiazenylnaphthalen-1-yl)diazenyl]phenol Chemical compound C1=CC(O)=CC=C1N=NC(C1=CC=CC=C11)=CC=C1N=NC1=CC=CC=C1 FWTBRYBHCBCJEQ-UHFFFAOYSA-N 0.000 claims description 4
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 4
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- 239000001000 anthraquinone dye Substances 0.000 claims description 4
- ILZWGESBVHGTRX-UHFFFAOYSA-O azanium;iron(2+);iron(3+);hexacyanide Chemical compound [NH4+].[Fe+2].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ILZWGESBVHGTRX-UHFFFAOYSA-O 0.000 claims description 4
- 239000000987 azo dye Substances 0.000 claims description 4
- 239000004203 carnauba wax Substances 0.000 claims description 4
- 235000013869 carnauba wax Nutrition 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 4
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 150000002193 fatty amides Chemical class 0.000 claims description 4
- 229920006270 hydrocarbon resin Polymers 0.000 claims description 4
- 238000007603 infrared drying Methods 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 229940099800 pigment red 48 Drugs 0.000 claims description 4
- 229940067265 pigment yellow 138 Drugs 0.000 claims description 4
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 239000003784 tall oil Substances 0.000 claims description 4
- 235000010215 titanium dioxide Nutrition 0.000 claims description 4
- 239000001018 xanthene dye Substances 0.000 claims description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000295 fuel oil Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 150000003626 triacylglycerols Chemical class 0.000 claims description 3
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 claims description 3
- FYYZTOOGFNLGII-UHFFFAOYSA-N (1,6-dihydroxy-1-prop-2-enoyloxyhexyl) prop-2-enoate Chemical compound OCCCCCC(O)(OC(=O)C=C)OC(=O)C=C FYYZTOOGFNLGII-UHFFFAOYSA-N 0.000 claims description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 claims description 2
- LNBMZFHIYRDKNS-UHFFFAOYSA-N 2,2-dimethoxy-1-phenylethanone Chemical compound COC(OC)C(=O)C1=CC=CC=C1 LNBMZFHIYRDKNS-UHFFFAOYSA-N 0.000 claims description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 2
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical class C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 claims description 2
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 claims description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 2
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 2
- IKVYHNPVKUNCJM-UHFFFAOYSA-N 4-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C(C)C)=CC=C2 IKVYHNPVKUNCJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 claims description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 2
- 150000008062 acetophenones Chemical class 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
- BFYJDHRWCNNYJQ-UHFFFAOYSA-N oxo-(3-oxo-3-phenylpropoxy)-(2,4,6-trimethylphenyl)phosphanium Chemical compound CC1=CC(C)=CC(C)=C1[P+](=O)OCCC(=O)C1=CC=CC=C1 BFYJDHRWCNNYJQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 claims description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 2
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- 239000003549 soybean oil Substances 0.000 claims description 2
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- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims 6
- 239000003960 organic solvent Substances 0.000 claims 4
- 238000007385 chemical modification Methods 0.000 claims 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims 2
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 claims 1
- SOBZYRBYGDVKBB-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO.OCC(CO)(CO)CO SOBZYRBYGDVKBB-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 15
- 239000011256 inorganic filler Substances 0.000 abstract description 5
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 5
- 235000010446 mineral oil Nutrition 0.000 abstract description 3
- 238000004945 emulsification Methods 0.000 description 26
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- 239000004606 Fillers/Extenders Substances 0.000 description 23
- 239000000839 emulsion Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 11
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- 238000012360 testing method Methods 0.000 description 11
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- 238000010348 incorporation Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- 238000000518 rheometry Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 238000007645 offset printing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
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- 239000011888 foil Substances 0.000 description 4
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- 239000007787 solid Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000005276 aerator Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
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- 239000000080 wetting agent Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- XQAVYBWWWZMURF-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO XQAVYBWWWZMURF-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003924 oil dispersant Substances 0.000 description 1
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/108—Hydrocarbon resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/023—Emulsion inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Definitions
- the present invention relates to lithographic printing inks characterized by comprising substantial quantities of both water and inorganic filler.
- the present invention also relates to means to stabilize the included water as a stable emulsion.
- emulsified phase contains water and a polyol.
- US 6140392 to Kingman et al . also discloses single fluid printing inks suitable for waterless offset lithography, wherein the continuous phase includes an acid- functional vinyl resin and the discontinuous (emulsified) phase a polyethylene glycol.
- US2004/0013983 to Lee et al . teaches the importance of selecting a surfactant of the appropriate hydrophobicity hydrophilicity balance (HLB) for a stable emulsion in single fluid inks.
- HLB hydrophobicity hydrophilicity balance
- WO2004/045863 to Battersby et al discloses a planographic printing apparatus and method utilizing a single fluid lithographic ink and special pH-neutral plate cylinder .
- VOC VOC of that ink.
- VOC is harmful to air quality and detrimental to the environment of a print shop, most especially to the printers who must operate the printing presses.
- some lithographic inks for example web offset heatset inks, contain between 30 and 45% VOC. Another is to reduce the cost of the raw materials per unit weight of ink.
- Inks suitable for lithographic printing also frequently include extenders or fillers as a component.
- extenders or fillers include bentonite, montmorillonite and kaolin clays, calcium carbonate and other inorganic materials, are known to those skilled in the art as a means to reduce the amount of expensive pigments and colorants required in an ink to achieve a particular printing
- the present invention provides for an ink
- the present invention also provides for an ink comprising :
- the present invention further provides for an energy-curable ink comprising:
- the present invention also provides for a process for manufacturing the inks of this invention, comprising the step of:
- the present invention further provides for a process for manufacturing the energy-curable inks of this invention, comprising the steps of:
- the present invention also provides for a process of offset lithographic printing, comprising the steps of printing any the inks of this invention onto a substrate, then curing said ink with one or more of the means selected from a group comprising: actinic radiation, electron beam, heat, infra-red, and air-drying, to form a dry ink film on said substrate.
- the present invention further provides for a printed article produced by the method of printing any of the inks of this invention onto a substrate.
- a novel lithographic printing ink comprising 10 - 40% by weight of water and 8 - 15% by weight of inorganic filler and further comprise at least one resin and at least one pigment or colorant suitable for the making of a lithographic ink.
- the inks of our invention comprise 20 - 40% by weight of water and 10 - 15% by weight of filler or extender.
- the inks of our invention comprise 30 - 40% water by weight and 10 - 15% of filler or extender by weight.
- a novel lithographic printing ink comprising 10 - 30% by weight of inorganic filler and 1 - 10% by weight of water and further comprising at least one resin and at least one pigment or colorant suitable for the making of a lithographic ink.
- the inks of our invention comprise 4 - 10% of water by weight and 20 - 30% of filler or extender by weight.
- filler comprise 4 - 10% of water by weight and 25 - 30% of filler or extender by weight.
- a novel energy-curable lithographic printing inks comprising 2 - 20% by weight of water and 3 - 10% by weight of inorganic filler, together with one or more pigments or colorants and one or more photocrosslinkable materials.
- the energy- curing inks of our invention comprise 6 - 20% by weight of water and 3 - 10% by weight of extender or filler.
- Said method can include the incorporation of an emulsifying agent into the ink/water emulsion, to provide an appropriate level of ease of formation of the ink/water emulsion, maintain its stability in storage and yield optimal print and dry film performance when the ink is printed.
- This invention is not limited to the use of a particular emulsifying agent, and, advantageously, a combination of two or more different emulsifying agents may be employed.
- the pre-emulsification of water allows for a more even distribution of the water within the ink. This way, the ink/water equilibrium on press is achieved more rapidly and more thoroughly which results in better transfer and less misting, due, in part, to the cooling effect the evaporating water gives to the printed surface and which contributes also to a cleaner and healthier press room environment.
- Said emulsifying agents may include non-water soluble materials. Stable water in oil micro-emulsions of offset lithographic inks have been described in the prior art, above. These offer many advantages over non-emulsified inks, including but not limited to lower VOC, better misting, and lower water demand. However, under high shear press conditions micro-emulsions made with conventional surface active agents are often not sufficiently stable. This leads to press problems such as loss of color density due to poor transfer, and in extreme cases, complete loss of image due to stripping. It has now been discovered that, employing the emulsification process of the present invention, inks that are stable under high pressure during the print process can be produced.
- incorporation of said emulsifying agents is performed under controlled pH conditions.
- the pH ranges for optimal quality are tied to the emulsifying agent type and are pH 8.0 - 9.5 and 4.0 - 5.5.
- a further practical advantage when employing the inks of our invention is reduced waste substrate, for example newsprint paper, due to shorter press start-up times.
- Lithographic printing inks especially those designed for offset printing, were prepared to include simultaneously high amounts of water and high amounts of an inorganic particulate material, termed a "filler" or
- the extender is selected from calcium carbonate, clay (including bentonite,
- montmorillonite and kaolin clay montmorillonite and kaolin clay
- talc montmorillonite and kaolin clay
- magnesium carbonate and silica or combinations thereof.
- said filler is a calcium carbonate or a kaolin clay and is in a particulate form wherein the mean particle size of the particles is 1.4 microns or less.
- a dispersant can be used to disperse the clay or other filler employed.
- a preferred class of materials, suitable for air- or heat- drying lithographic inks, is modified soy oil dispersants.
- absorption potential as well as the nature of the other raw materials comprising the printing ink.
- the latter are selected according to whether the ink is designed for coldset, heatset or sheetfed offset printing, as is well- known to those skilled in the art.
- filler at a very high loading has to be carefully formulated for intrinsic ink properties. Lithographic printing inks require a carefully controlled and high level of tack.
- Tack is a lithographic ink property that needs to be tailored for the substrate that is being printed on. For example, a lower tack is needed to print on uncoated newsprint stock versus, for example, a coated paper, in order to avoid picking ("picking" is the removal of an already-printed ink by another ink during a multicolor print process) and substrate web breaks. Ink viscosity preferably should be at the highest viscosity per unit tack. Tack is conveniently measured using an electronic inkometer with a water bath maintained at 90 ⁇ 0.5°F. [000032] In addition, ink strength, leading to the printed colorimetric optical density of the dried ink film, needs to be appropriate for the paper.
- the ink film may be too thin, creating in turn conditions where ink picking may become a problem.
- Fillers and extenders are also well-known to those skilled in the art to be valuable components of a lithographic ink to optimize ink misting and flinging, and water uptake during interaction with fount solution.
- the amount of water which may be incorporated into a printing ink and the stability of the emulsified water within that ink may also be enhanced by the use of suitable emulsification aiding additives.
- the stability of the water-in-oil emulsion remain high throughout manufacture, storage and shipping, and during the printing process. In particular this requires that there be no phase separation of the emulsion under influence of high shear and high pressure.
- the high shearing of lithographic printing inks is a feature of the environment that they must experience, both during manufacture, and when the ink is transferred from ink ducts to the printing plate down a roller train. The target of this novel ink system is to exhibit
- lithographic inks not benefitting from both water and filler addition.
- the properties of colorimetric optical density and ink mileage are not dependent to percentage of water addition but only upon the stability of the water-in- oil emulsion.
- Improved mileage reduced ink consumption
- Ink mileage is defined as the amount of ink needed to cover a specific area of substrate at a specific optical density. Improved mileage results in a reduction in ink consumption during the press run, which is an economic benefit to the printer. Mileage may be measured and calculated, for example, from the density curves based on laboratory prints, for heatset and sheetfed inks, on APCO paper with a beaubau Printability Tester. It may also be conveniently be assessed, for coldset inks, by printing onto 27.7#
- the substrate is dried using the Sinvatrol heatset dryer. Density may be recorded using an X-Rite spectrodensitometer . The amount of ink required to achieve an equal density, as determined by weighing on an analytical balance, determines relative the mileage. A lower weight at an equal density would equate to improved mileage.
- the inks of this invention maintain their cohesion and transferability Unstable emulsified lead to press problems such as stripping and loss of color control.
- a further benefit of being able to maintain, at minimum, optical density and mileage with inclusion of substantial amounts of water and filler is that the organic content of the printing inks is reduced. This is a benefit, as described above, both for VOC reduction and for limiting the presence of materials like mineral oils that can subsequently cause issues with taint in foodstuffs.
- the incorporation of water into the printing inks of this invention can be optimized by the appropriate selection of different emulsification agents, each having an optimal pH of incorporation. It is thus a feature of this invention that, to optimize the amount of water being incorporated into the printing ink, to maximize all stated benefits hereinbefore delineated, the individual aqueous emulsifying agent solutions must be admixed into the ink matrix serially in order to avoid poor emulsion stability caused by simultaneously adding emulsification agents of differing optimal pH value all at once.
- a particularly effective addition scheme that it has been found is: firstly, to employ an emulsifying agent best suited to mild alkaline solution (optimum pH range 8.0 through 9.5), then, secondly, to employ an emulsifying agent best suited to mild acidic conditions (pH 4.0 through 5.5), then if necessary, a third and final deployment of an emulsifying agent best suited to mild alkaline solution (optimum pH range 8.0 through 9.5) .
- the scheme is important to avoid gums such as gum Arabic to separate, when these natural gums is used as one of the emulsification agents.
- This platform approach can be applied to all types of offset inks and will provide pressure stable emulsions with no loss of colorimetric optical density or ink mileage.
- Suitable emulsifying agent include, but are not limited to, a salt of tall oil fatty acid, dimer acid, a polyalkylene oxide surfactant, ambergum, gum Arabic, a maleated fatty ester, a maleated fatty amide and a dioleate, preferably a poly(alkyene oxide) dioleate or a modified sugar dioleate.
- a further benefit deriving from the printing inks of this invention is found in reduced piling on the blanket during the lithographic offset printing process.
- "Piling” is defined as the build-up of pigment particles and paper fibers upon the blanket or printing plate, caused by the inability of the ink to transfer through the press. It has been found that the inks of the present invention are improved in their tendency to pile. This is seen by the reduction in the number of blanket washes necessary when employing the inks of the present invention on a printing press. It has been found that the time between blanket washes was on average, doubled, in comparison to employing conventional printing inks.
- Piling may also be assessed on a visual basis and rated as 1-10, with 1-3 being minimal or slight piling; 4-6 being moderate piling; and 7-10 being severe piling.
- Suitable resins for lithographic ink design include, but are not limited to, hydrocarbon resins, hybrid resins (hydrocarbon/rosin blend), aldehyde resins, maleic modified rosin ester, alkyds, phenolic modified rosin ester, and others well-known to those skilled in the art, for conventional lithography.
- Suitable oils and solvents may include, but are not limited to mono-, di-, or tri-glycerides liquid at 25°C, heavy oils, hydrocarbon distillates, and mineral oils.
- Suitable waxes for the inks of this invention include, but are not limited to amide wax, erucamide wax, polypropylene wax, paraffin wax, polyethylene wax,
- polytetrafluoroethylene polytetrafluoroethylene, carnauba wax, and combinations thereof .
- additives contained in inks or coatings typically are surface-active agents, waxes, shelf-life stabilizers, etc. and combinations thereof. These additives may function as leveling agents, shelf-life stabilizers, wetting agents, slip agents, flow agents, dispersants and de-aerators. Additional to waxes, as disclosed
- preferred additives include surfactants, including fluorocarbon, silicone and organic monomeric and polymer types. Said additives may further include
- emulsifying agents including those hereinbefore mentioned.
- acrylic monomers used in the inks of the present invention are preferably esters of acrylic acid with a defined structure, a functionality of greater or equal to 2, having a weight number average of 200-800 Daltons, which impart curing speed, solvent resistance, hardness and allow viscosity adjustment.
- a non-limiting list of examples of acrylate monomers and oligomers suitable in inks of this invention include 1,2-ethylene glycol diacrylate, 1 , 4-butandiol diacrylate, 1 , 6-hexandiol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylates, propoxylated neopentyl glycol diacrylates, tripropylene glycol diacrylate, bisphenol-A diacrylate, ethoxylated bisphenol-A-diacrylates , bisphenol- A-diglycidyl ether diacrylate, ethoxylated bisphenol-A- diacrylates, poly (ethylene) glycol diacrylates, trimethylol propane triacrylate, trimethylol propane trimethacrylate, ethoxylated trimethylol propane triacrylates, propoxylated trimethylol propane triacrylates, propoxylated glyce
- An acrylic oligomer used in the inks of this invention is preferably a prepolymer with a weight number average of 400-3000 Daltons, an acrylate functionality greater or equal to 2, such as for example epoxy acrylates, polyester acrylates, acrylated polyurethanes , acrylated polyacrylates , acrylated polyethers, acrylated epoxidized oils based on linseed oil and soybean and castor oil and mixtures thereof. It imparts rheology, pigment wetting, transfer, gloss, chemical resistance and other film
- non-curable resins having no curable acrylic groups such as polyacrylates , polyesters, polyurethanes , polyamides, ketone resins, aldehyde resins, alkyd resins, phenol-formaldehyde resins, rosin resins, hydrocarbon resins, alkyd resins or mixtures of the
- such inert resins will have a number average molecular weight of between 1,000 and 30,000 Daltons, and most preferably number average molecular weight of between 1,000 and 4,000 Daltons.
- Such resins may reduce shrinkage, improve adhesion, pigment wetting, gloss, rheology, flexibility, and usually, solid, "hard” resins are dissolved in acrylic monomers, such as trimethylol propane triacrylate and added to the premix of raw
- the energy curable inks of the present invention may contain one or more colorants in the form of a dye or pigment dispersed
- the energy-curable inks of the present invention may contain, if cured by UV-light, photo initiators, such as for example benzophenones , benzilketals , dialkoxy acetophenones , hydroxyalkyl acetophenones ,
- thioxanthones for example benzophenone, methyl
- benzophenone 4-phenylbenzophenone, 4,4'- bis (dimethylamino) -benzophenone, 4,4' -bis (diethylamino) - benzophenone, 2 , 2-dimethoxy-2-phenylacetophenone, dimethoxy acetophenone, diethoxy acetophenone, 2-hydroxy-2-methyl-l- phenylpropan-l-one, 2-benzyl-2-dimethylamino-l- (4- morpholinophenyl ) -butan-l-one, 2-methyl-l- [4 (methoxythio) - phenyl ] -2-morpholinopropan-2-one, diphenyl acylphenyl phosphine oxide, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2 , 4 , 6-trimethylbenzoylethoxyphenyl phosphine oxide, 2-isopropylthioxantone,
- lithographic printing inks which are of the so-called “hybrid” type, that is, may be cured by a plurality of means including but not limited to aerial oxidation, ambient temperature drying, absorption into a substrate, heat, infra-red radiation, actinic radiation, and electron beams, may contain raw materials suitable both for
- Colorants suitable for use in the inks of the present invention include conventional dyes and organic or inorganic pigments.
- Dyes include but are not limited to azo dyes, anthraquinone dyes, xanthene dyes, azine dyes, and combinations thereof.
- Representative pigments may, for example, be selected from the group of Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 63, Pigment Yellow 65, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 75, Pigment Yellow 83, Pigment Yellow 97, Pigment Yellow 98, Pigment Yellow 106, Pigment Yellow 111, Pigment Yellow 114, Pigment Yellow 121, Pigment Yellow 126, Pigment Yellow 127, Pigment Yellow 136, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 174, Pigment Yellow 176, Pigment Yellow 188, Pigment Yellow 194, Pigment Orange 5, Pigment Orange 13, Pigment Orange 16, Pigment Orange 34, Pigment Orange 36, Pigment Orange 61, Pigment Orange 62, Pigment Orange 64, Pigment Red 2, Pigment Red 9, Pigment Red 14, Pigment Red 17, Pigment Red 22, Pigment Red 23, Pigment Red 37, Pigment Red 38, Pigment Red 41, Pigment Red 42, Pigment Red 48: 2, Pigment Red 53
- additives for the purposes of optimizing ink performance for particular applications, including modifying flow, surface tension, gloss, flow, pigment wetting and abrasion resistance of the cured coating or printed ink.
- additives contained in inks or coatings typically are surface-active agents, waxes, shelf-life stabilizers, etc. and combinations thereof. These additives may function as leveling agents, shelf- life stabilizers, wetting agents, slip agents, flow agents, dispersants and de-aerators.
- Preferred additives include fluorocarbon surfactants, silicones and organic polymer surfactants.
- Tegorad product lines are trademarks and are commercially available products of Tego Chemie, Essen, Germany
- Solsperse product lines are trademarks and are commercially available products of Lubrizol Company
- Said additives may further include waxes, including those hereinbefore mentioned; emulsifying agents, including those hereinbefore mentioned; flow and further wetting aids, including but not limited to monomeric surfactants, and pigment and filler dispersing aids, including but not limited to modified soy oil.
- a particularly preferred group of inks are those characterized in that the ink shows a peak maximum of below -40°C for emulsified water, measured by differential scanning calorimetry (DSC) at a cooling rate of
- WO2004045863 directly to energy curable inks.
- hydrophilic, water-soluble materials such as alcohols, glycerol, glycol ethers, polyethylene glycol oligomers, acid functional acrylic resin and surfactants and emulsifiers and the like.
- These non-curable, liquid materials retard cure and can leave behind a smeary and tacky surface after drying if incorporated into an energy curable system.
- the use of emulsifiers in a typical energy curable lithographic ink should be used with care due to the influence on the water-ink balance and risk of over-emulsification .
- the inks of the present invention are made using typical procedures known in the art, usually by dry- grinding or using a flush.
- the required amount of dry pigment is mixed with resins and/or oils and/or acrylate monomers and and/or oligomers and additives on a mixer for 15-30 minutes to wet out all pigment.
- the pre-mix is then ground on a three roll mill until the desired grind specifications are met .
- the water for emulsification can be added to the pre-mix of raw materials before milling or preferably post- added to the finished ink at a post-blend station.
- water is stirred in after milling, rather than added before milling, the amount of emulsified water in the ink is more consistent, as the stirring condition can be better
- the emulsification of the ink with water is carried out with a stirrer introducing a good shear force into the ink.
- a stirrer introducing a good shear force into the ink.
- This can be a propeller stirrer, a dented dissolver plate, a centrifugal mixer or a tri- foiled butterfly mixer, among others.
- Preferred is a tri- foiled butterfly mixer for dispersion of highly viscous mixtures.
- the inks may increase in temperature. The temperature
- emulsification preferably would not exceed 60°C during the emulsification; otherwise a portion of the emulsified water can be lost by evaporation .
- monomers can be added to adjust rheology, tack and flow.
- the water in the ink is sufficiently finely emulsified. Assessment of the quality of
- Preferred is a viscosity of 20-50 PaS. Another useful procedure for the measurement of viscosity involves
- the emulsified inks of the present invention preferably show a flow of 1-15 cm on an inclined plate.
- An incline plate is a vertically (90°) fixed aluminum plate on which 1ml of ink is applied on top. Then, the distance is measured in which the ink runs down the plate within 15 minutes by gravity. Preferred is a flow of 4-8 cm.
- the emulsified inks of the present invention preferably show a tack of 200-400 units measured using a "Tack-o-Scope" instrument (Model 2001) from IGT Testing Systems, a company operating in the Netherlands, which is known to a person skilled in the art.
- a "Tack-o-Scope” instrument Model 2001
- emulsified water may evaporate from the tack-o-scope, a special method is applied. First, 1 ml of ink is distributed on the rubber roller and held at 30°C for 90 seconds at a roller speed of 50 rpm, then 30 seconds at 300 rpm. Then, the tack value is taken at a roller speed of 150 rpm.
- the preferred tack is 250-350 units.
- DSC differential scanning calorimetry
- scanning calorimeters are able to measure the amount of heat absorbed or released during such transitions.
- interfacial free water in an ink gives a sharp peak maximum around 0°C to -20°C in DSC, whereas finely emulsified water shows a broad peak with a peak maximum at -30 to -55° C.
- the target of the emulsification process is to provide inks having only peaks with maxima below -40°C in DSC.
- the integrated area under the peak (Joule/g) in the DSC is an indication of the amount of emulsified water in the ink. If more water is finely emulsified, the number for the
- the energy curable ink with 6% of emulsified water typically shows about three times the heat flow than the ink with 3% of water. No free water is detected (absence of peaks below -40°C) .
- the energy curable ink without emulsified water typically shows no signals.
- a particularly preferred group of inks are those characterized in that the ink shows a peak maximum of below -40°C for emulsified water, measured by differential scanning calorimetry (DSC) at a cooling rate of 10°C/minute.
- Emulsion stability of the inks of this invention was also evaluated at a pilot scale on a press simulator unit supplied by Mitsubishi Heavy Industries Ltd.
- the objective was to correlate the results with those obtained by DSC, that the emulsified water is very finely dispersed, so that there will be no phase separation under stress during the transport, the delivery procedure (pumps) and on press.
- the general litho suitability of the inventive inks can thus also be verified by this press simulator unit.
- This device can be considered as a single press unit that is run without paper by transferring the ink from the blanket cylinder to a metal cylinder where it is scraped off with a doctor blade. Apart from the missing paper, the ink is run under real print conditions and the same tests or observations like on a real press, for example water window, misting, etc., can be performed.
- the water window of the inks of this invention was comparable to the standard commercial inks.
- the scumming point minimum amount of water required to clear the non-image areas
- No water separation was observed in the ink trough or on the rollers. Full details are described below in the Examples.
- Freezing-point depression can be used as a means to get a qualitative understanding of droplet size
- the high amount of water in the inks of our invention is finely dispersed.
- finely dispersed water is much tighter bound into the ink system, this is an indication, borne out in practice by observing the ink over a lengthy time period, that there will be no water separation during handling and processing of the ink.
- Particularly preferred inks of the present invention are those which, when measured by the tests delineated above, show that the ink characterized in that the water in the ink is predominantly emulsified water with a ratio of emulsified water to free water of greater than 9:1, measured by the ratio of integrated areas of heat flow in differential scanning calorimetry at 0 to - 20°C and -30 to -60° C, measured with a cooling rate of 10°C/minute.
- the inks of the present invention are characterized in that the emulsified water is present at greater than 90% of the total water content of the ink, and that droplets of emulsified water have a size of less than 13 ⁇ m.
- Such inks are further characterized in that the inks exhibits an improved transfer of between 5-100% compared to the same formulation without emulsified water, measured by the collected ink on a Mitsubishi offset print simulator .
- the ink characterized in that the water in the ink is predominantly emulsified water with a ratio of emulsified water to free water of greater than 9:1, measured by the ratio of integrated areas of heat flow in differential scanning calorimetry at 0 to - 20°C and -30 to -60° C, measured with a cooling rate of 10°C/minute.
- the inks of this invention may be printed on a wide range of substrates, including but not limited to those composed of any typical substrate material such as paper, plastics, metals, and composites.
- the substrate may be paper print stock typically used for publications or may be a packaging material in the form of a cardboard sheet or corrugated board, aluminum foil, a container such as a bottle or can, or the like.
- the substrate may be paper print stock typically used for publications or may be a packaging material in the form of a cardboard sheet or corrugated board, aluminum foil, a container such as a bottle or can, or the like.
- packaging material is a polyolefin, such as a polyethylene (PE) or a polypropylene (PP) , a polyester such as
- PET polyethylene terephthalate
- metalized foil such as an laminated aluminum foil, a metalized polyester, or a metal container.
- the inks of this invention that are designed to be energy-curable are further characterized in that the inks have less than 6% of emulsified water and do not contain water-soluble inorganic salts or emulsifiers with a hydrophilicity lipophilicity balance (HLB) value of 2-18 and do not contain water-soluble monomers or water- soluble resins.
- HLB hydrophilicity lipophilicity balance
- an actinic light source such as for example UV-light, provided by a high-voltage mercury bulb, a medium-voltage mercury bulb, a xenon bulb, a carbon arc lamp, a metal halide bulb, a UV-LED lamp or sunlight.
- the wavelength of the applied irradiation is preferably within a range of about 200 to 500 nm, more preferably about 250 to 350 nm.
- UV energy is preferably within a range of about 30 to 3000 mJ/cm 2 , and more preferably within a range of about 50 to 500 mJ/cm 2 .
- the bulb can be appropriately selected according to the absorption spectrum of the radiation curable composition.
- the inks of the present invention can be cured under inert conditions .
- the radiation curable inks of this invention can be cured by electron beam (EB) .
- EB-dryers are available for example from Energy Science, Inc. of Wilmington, Mass, or from Advanced Electron Beams Inc. (AEB) of Wilmington, Mass.
- the energy absorbed, also known as the dose, is measured in units of kiloGrays (kGy) , one kGy being equal to 1,000 Joules per kilogram.
- the electron beam dose should be within the range of 10 kGy to about 40 kGy for complete curing.
- a radiation dose of 20-30 kGy at an oxygen level of below 200 parts per million (ppm) is usually sufficient to get a dry, solvent resistant ink or coating.
- Gloss is a key parameter for the dried films of all classes of inks of this invention, and is conveniently measured with a Sheen glossmeter at 60° angle.
- Emulsifier solution 1 2,3 or 4 (pH 8.0 - 9.5) 2.
- Emulsifier solution 6 or 7 made from an intermediate 5 (pH 4.0 - 5.5)
- Emulsifier solution 8 (pH 8.0 - 9.5)
- Examples 5 - 20 [000091] demonstrate the utility of coldset in made according to the present invention.
- Table 18 shows the formulation of comparative yellow inks and inks of the present invention.
- Table 19 shows the preparation of the clay (filler) intermediate compound.
- Table 20 shows the formulation of comparative black inks and inks of the present invention.
- Table 21 shows the formulation of comparative cyan inks and inks of the present invention.
- Table 21 shows the formulation of comparative yellow inks and inks of the present invention.
- Table 23 shows the sources of raw materials employed to make the sixteen examples. The results clearly demonstrate that the inks of this invention possess tack and colorimetric optical density equivalent to standard inks, yet have greatly superior mileage, ranging from an improvement of 3.7% through 9.7%, depending on the ink color and levels of both water and filler.
- Soy oil, BHT solution and dispersant were added to a mixing vessel. Clay was added under continuous feed under low shear mixing. Once clay has been added, the compound was mixed under high shear until homogenous.
- Compound is then subjected to a Schold shot mill charged with 3/32 carbon steel shot and milled until dispersed to a mean micron size of about 1.4 microns.
- the transferred ink on the ductor roller is scraped off for a defined time and the collected ink is measured on a laboratory balance.
- the temperature increased up to 45-55°C.
- Tack Measured with calibrated "Tack-o-scope” instrument (Model 2001) from IGT testing systems, Netherlands. 1 ml of ink is placed on the EPDM rubber distribution roller 30°C, distributed for 90 seconds at a roller speed of 50 rpm, then 30 seconds at 300 rpm. Then the tack value is taken at a roller speed of 150 rpm.
- Peak maximum of emulsified water in DSC
- sample was measured into an aluminum-pan. Ink should be in the middle of the aluminum-pans, not on upper end of the walls.
- the pan is closed with a lid and sealed with the
- the pan is placed into the measuring cell.
- a second empty Al-pan is placed into the reference cell.
- the sensitivity of the measurement cell is set to 100%.
- Step 1 cool with a rate of 10K/min. to -80°C under Nitrogen sparge ( ⁇ 20-25mL/min . ) ;
- Step 2 re-heating with a rate of lOK/min. to 25°C under nitrogen sparge ( ⁇ 20-25mL/min . )
- the inks of Table 24 were produced as in the general principle delineated in Table 25. As an example of the general preparation, the preparation of three cyan lithographic inks is illustrated. These were made on a three roll mill under a roller pressure of 12 atmospheres
- Example 41 of water was emulsified.
- Example 39 is
- Examples 40 and 41 which contain emulsified water, show increased transfer of ink) , as measured by the Mitsubishi offset print simulator versus the non-emulsified comparative Example 39.
- Examples 42-45 show increased transfer of ink
- Example 43 and 45 inks were also tested on a Didde Offset Web press (GSS, Graphic Systems Services) . Again, the emulsified inks showed improved transfer as indicated by the reduced ink duct settings to get the same optical density (inks notches vs. the Standard) . The optical density is measured by an online densitometer installed on the Didde press and confirmed later by a
- Viscosity, tack and flow are measured as aforementioned. As shown in the table above the emulsified ink shows an increased transfer.
- Table 29 shows standard yellow inks versus those of this invention
- table 30 shows standard magenta inks versus those of this invention
- Table 31 shows standard cyan inks versus those of this invention.
- the intermediate compounds described in tables 29 through 31 were prepared as shown in table 17.
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- Organic Chemistry (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (5)
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US201261660159P | 2012-06-15 | 2012-06-15 | |
US201261726172P | 2012-11-14 | 2012-11-14 | |
US201361773204P | 2013-03-06 | 2013-03-06 | |
US201361789226P | 2013-03-15 | 2013-03-15 | |
PCT/US2013/045845 WO2013188746A2 (en) | 2012-06-15 | 2013-06-14 | Lithographic offset inks with water and filler content |
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EP2861632A2 true EP2861632A2 (en) | 2015-04-22 |
EP2861632A4 EP2861632A4 (en) | 2016-04-20 |
EP2861632B1 EP2861632B1 (en) | 2021-09-01 |
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JP (1) | JP6243415B2 (en) |
CN (1) | CN104507977B (en) |
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IN (1) | IN2014DN10501A (en) |
TW (1) | TW201412891A (en) |
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JP2015003949A (en) * | 2013-06-19 | 2015-01-08 | Dicグラフィックス株式会社 | Water-containing offset ink |
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US10113076B2 (en) * | 2014-09-30 | 2018-10-30 | Xerox Corporation | Inverse emulsion acrylate ink compositions for ink-based digital lithographic printing |
JP6401572B2 (en) * | 2014-10-21 | 2018-10-10 | Dicグラフィックス株式会社 | Printing ink composition and printed matter |
JP2016098352A (en) * | 2014-11-26 | 2016-05-30 | Dicグラフィックス株式会社 | Printing ink composition |
US9416285B2 (en) | 2014-12-17 | 2016-08-16 | Xerox Corporation | Acrylate ink compositions for ink-based digital lithographic printing |
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TW201707778A (en) * | 2015-05-21 | 2017-03-01 | 盧伯利索先進材料有限公司 | Emulsion composition for energy curable ink compositions and a printing process and method thereof |
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TW201720881A (en) * | 2015-09-17 | 2017-06-16 | Toray Industries | Lithographic printing ink, varnish for lithographic inks, and method for producing printed matter using said ink |
US20180051183A1 (en) * | 2016-08-17 | 2018-02-22 | Xerox Corporation | Seven-color ink set for a digital advanced lithographic imaging process |
CN106947314B (en) * | 2017-03-28 | 2018-03-30 | 深圳市容大感光科技股份有限公司 | A kind of printed circuit board (PCB) character marking ink composite and wiring board |
AU2018344119B9 (en) * | 2017-10-02 | 2020-10-08 | Dic Graphics Corporation | Electron beam-curable water-based flexo ink for surface printing and boilable/retort pouch using same |
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CN109634074A (en) * | 2019-01-18 | 2019-04-16 | 湖北鼎龙控股股份有限公司 | A kind of novel toner and preparation method thereof |
CN113710755B (en) * | 2019-04-18 | 2023-10-13 | 太阳化学公司 | Low migration electron beam curable primer |
CN110157239A (en) * | 2019-06-12 | 2019-08-23 | 浙江中烟工业有限责任公司 | Recessed sand oil of a kind of online volume of EB and preparation method thereof |
CN114945637B (en) | 2019-12-20 | 2023-10-13 | Dic株式会社 | Pigment composition, active energy ray-curable offset ink, and method for producing pigment composition |
CN111334116A (en) * | 2020-03-31 | 2020-06-26 | 吴永淇 | Environment-friendly printing ink |
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CN102746730B (en) * | 2012-05-29 | 2013-12-11 | 兰州理工大学 | Aqueous alkyd acrylic resin printing ink and preparation method thereof |
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EP2861632A4 (en) | 2016-04-20 |
WO2013188746A2 (en) | 2013-12-19 |
EP2861632B1 (en) | 2021-09-01 |
TW201412891A (en) | 2014-04-01 |
WO2013188746A3 (en) | 2014-02-13 |
JP2015525279A (en) | 2015-09-03 |
JP6243415B2 (en) | 2017-12-06 |
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CN104507977A (en) | 2015-04-08 |
IN2014DN10501A (en) | 2015-08-21 |
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